Synthesis and characterization of 9-(4-nitrophenyl)-3,3,6,6-tetramethyl-3, 4,6,7,9,10-hexahydro-1,8(2H,5H) acridinedione and its methoxyphenyl derivative

Article abstract of DOI:10.1007/s10870-005-3880-2

9-(4-Nitrophenyl)-3,3,6,6-tetramethyl-3,4,6,7,9,10-hexahydro-1,8(2H,5H) acridinedione (NTHA) crystallizes in orthorhombic space group P2 ₁2₁2₁ with a = 5.9716(1) A, b = 18.0476(3) A, c = 19.2445(2) A, V = 2074.04(5) A³, Z = 4, D _cal = 1.263 Mg m^-3 and R = 0.0521 (wR = 0.1326) for 4078 observed reflections. 9-(4-Nitrophenyl)-10-(4-methoxyphenyl)-3,3,6,6- tetramethyl-3,4,6,7,9,10-hexahydro-1,8(2H,5H) acridinedione NMTHA, crystallizes in monoclinic space group P2₁/c with a = 15.669(5) A, b = 10.652(4) A, c = 18.337(6) A, β = 108.25(1)°, V = 2906.66(2) A³, Z = 4, D _cal = 1.245 Mg m ^-3 and R = 0.0725 (wR = 0.1847) for 5105 observed reflections. The experimental values are compared with the theoretical values calculated based on the semiemperical methods. The structures are stabilized by N-H...O and C-H...O types of intermolecular interactions in addition to van der Waals forces.

Full text of DOI:10.1007/s10870-005-3880-2

Journal of Chemical Crystallography, Vol. 35, No. 10, October 2005 (ꢀC 2005)
DOI: 10.1007/s10870-005-3880-2
Synthesis and characterization of 9-(4-nitrophenyl)-
3
,3,6,6-tetramethyl-3,4,6,7,9,10-hexahydro-1,8(2H,5H)
acridinedione and its methoxyphenyl derivative
(
1)
(2)
(1)
(1)∗
K. Palani, D. Thirumalai, P. Ambalavanan, M.N. Ponnuswamy,
(2)
and V.T. Ramakrishnan
Received July 30, 2004; accepted March 4, 2005
9
-(4-Nitrophenyl)-3,3,6,6-tetramethyl-3,4,6,7,9,10-hexahydro-1,8(2H,5H) acridinedione
˚
(
1
NTHA) crystallizes in orthorhombic space group P212121 with a = 5.9716(1) A, b =
˚
˚
˚ 3
−3
8.0476(3) A, c = 19.2445(2) A, V = 2074.04(5) A , Z = 4, Dcal = 1.263 Mg m
and R = 0.0521 (wR = 0.1326) for 4078 observed reflections. 9-(4-Nitrophenyl)-10-
(4-methoxyphenyl)-3,3,6,6-tetramethyl-3,4,6,7,9,10-hexahydro-1,8(2H,5H) acridinedione
˚
NMTHA, crystallizes in monoclinic space group P21/c with a = 15.669(5) A, b =
˚
˚
◦
˚ 3
1
0.652(4) A, c = 18.337(6) A, β = 108.25(1) , V = 2906.66(2) A , Z = 4, Dcal =
−3
1.245 Mg m and R = 0.0725 (wR = 0.1847) for 5105 observed reflections. The
experimental values are compared with the theoretical values calculated based on the
semiemperical methods. The structures are stabilized by N--- H· · ·O and C--- H· · ·O types
of intermolecular interactions in addition to van der Waals forces.
KEY WORDS: Crystal structure; conformation; semiempirical; hydrogen bondings; acridinediones.
Introduction
responsible for their activities in part. The inter-
calation hypothesis suggests that the planar aro-
9
The synthesis of 1,8-acridinediones has
matic ring system of the acridinediones become
inserted (intercalated) in between two adjacent
base pairs of a double-stranded nucleic acid.
In view of the above importance, the com-
attracted the chemists for quite sometime owing
to its pharmacological activities on this family of
compounds. These acridinediones are found to
possess a wide spectrum of biological properties
pounds
9-(4-nitrophenyl)-3,3,6,6-tetramethyl-
1
2
such as anti-tumour, antibacterial, antiamoe-
3,4,6,7,9,10-hexahydro-1,8(2H,5H) acridindione
(NTHA) and its 10-methoxy phenyl derivative
(NMTHA) are prepared and characterized by
different methods.
3
4
bic, hypertensive and anti-inflammatory.
The interactions of acridinediones with nu-
cleic acids are generally acknowledged to be
5–8
The structural properties of these 1,8-
acridinediones, namely NTHA and NMTHA are
also studied by semiempirical (AM1, PM3) meth-
ods. The theoretically calculated values are com-
pared with those derived from X-ray diffraction
methods.
(
1)
2)
Department of Crystallography and Biophysics, University of
Madras, Guindy Campus, Chennai 600025, India.
Department of Organic Chemistry, University of Madras, Guindy
Campus, Chennai 600025, India.
(
∗
To whom correspondence should be addressed; e-mail: mnpsy@
hotmail.com; crystal@giasmd01.vsnl.net.in.
7
51
1
074-1542/05/1000-0751/0 ꢀC 2005 Springer Science+Business Media, Inc.

752
Palani, Thirumalai, Ambalavanan, Ponnuswamy, and Ramakrishnan
This comparative study enables one to eval-
out with anisotropic thermal parameters for all
non-hydrogen atoms. The geometrical parameters
uate the validity of the theoretical methods to
predict the geometrical features of acridine-
dione systems and apply to different activity
studies.
13
were calculated by PARST and the molecular
14
graphics were drawn using ZORTEP.
Experimental
Synthesis
ꢁ
2,2 -(4-nitro-
General
NTHA. A
mixture
of
benzylidene) bis (5,5-dimethylcyclohexane-
1,3-dione) (1 g, 2.4 mmol) and ammonium
acetate (3 g, 39 mmol) in acetic acid (20 ml)
was refluxed for 6 h. The reaction mixture was
cooled, poured into ice and the separated solid
was filtered and recrystallized from a mixture a
chloroform-methanol (5:1).
NMTHA. A mixture of 2,2 -(4-nitro-
benzylidene) bis (5,5-dimethylcyclohexane-1,3-
dione) (1 g, 2.4 mmol) and p-anisidine (0.3 g,
The IR spectra were measured with
Shimadzu FTIR 8300 instrument as potassium
1
13
bromide pellets. The H and C NMR spectra
were recorded on Jeol-GSX400 (400 MHz) and
DPX 200 (200 MHz) instruments. Mass spectra
were obtained with Jeol-JMS-DX-303 HF.
Semiempirical calculations (AM1 and PM3)
were carried out using the MOPAC 6.0 molecular
orbitals set.
ꢁ
2.4 mmol) in acetic acid (20 ml) was refluxed for
X-ray crystal structure
6 h. The mixture was cooled, poured into ice and
the separated solid was filtered and recrystallized
from chloroform.
Crystals of NTHA and NMTHA were grown
by slow evaporation method from ethanol solution
at room temperature. Well-shaped crystals were
chosen for X-ray diffractometric measurements
on a Siemens SMART CCD area detector with
graphite monochromated MoKα radiation. The
entire data collection was covered over a hemi-
sphere of reciprocal space by a combination of
three sets of exposures each having a different
9-(4-Nitrophenyl)-3,3,6,6-tetramethyl-
3,4,6,7,9,10-hexahydro-1,8(2H,5H)
acridinedione (NTHA)
10
◦
Yield 0.82 g (87%); mp 258–260 C, IR
(KBr): 3433 (N---H), 1648 (C -- -- -- O), 1486, 1367,
◦
−1
1
φ angle (0, 88, and 180 ) for the crystal and
each exposure time of 10 s covered 0.3 in ω.
1229 cm . H NMR (CDCl , 400 MHz): δ
3
◦
0.93 & 1.08 (2s, 12H, gemdimethyl), 2.05–2.22
The crystal-to-detector distance was 4 cm and the
(ABq, 4H, J = 16.11 Hz, C ---CH ), 2.33–2.45
2
2
◦
detector swing angle was −35 . Crystal decay
(ABq, 4H, J = 17.09 Hz, C ---CH ), 5.05 (s,
4
2
was monitored by repeating thirty initial frames
at the end of the data collection and analyzing
the duplicate reflections, and was found to be
negligible.
1H, C ---H), 7.47–8.03 (2d, 4H, J = 8.79 Hz,
9
13
Ar---H) and 9.12 (s, 1H, NH). C NMR (CDCl ,
3
100 MHz): δ 25.93, 28.38, 31.34, 33.33, 39.55,
49.52, 110.34, 121.88, 127.91, 144.65, 148.76,
+
Structure solutions were carried out by di-
rect methods for both the compounds using
153.56, and 193.95. Mass m/z (%) 394 (M ,
2), 393(1), 378(1), 365(1), 335(2), 272(2),
271(4), 256(trace), 236(trace), 194(100), 180(66),
152(10), 138(16), 112(22) and 83(9). Analysis
calculated for C H N O (394.46): C, 70.03;
11
12
SHELXS97 and refined by SHELXL97. The
solvent molecule ethanol appeared at the adja-
cent site of the nitrogroup. Hydrogen atoms were
placed at the calculated positions but not refined.
Full-matrix least-squares refinement was carried
23
26
2
4
H, 6.59; N, 7.10; Found: C, 69.66; H, 6.84; N,
6.98.

Crystal structures of two acridinedione derivatives
753
Scheme 1.
9-(4-Nitrophenyl)-10-(4-methoxyphenyl)-
3,3,6,6-tetramethyl-3,4,6,7,9,10-hexahydro-
1,8(2H,5H) acridinedione (NMTHA)
8.4 Hz, Ar---H) and 7.56–8.10 (ABq, 4H, J =
13
8.8 Hz, Ar---H). C NMR (CDCl , 50 MHz):
3
δ 26.68, 29.61, 32.32, 33.58, 41.77, 50.00, 55.60,
1
13.41, 115.15, 123.39, 128.26, 128.79, 131.01,
◦
Yield 0.9 g (75%); mp 288–290 C; IR(KBr):
146.01, 150.99, 153.66, 159.98, and 195.66.
Mass m/z (%): 500 (M , 2), 499(trace), 472(2),
378(4), 236(2), 194(98), 180(100), 152(20),
138(30), 112(14) and 83(8). Analysis calcu-
lated for C H N O (500.58) C, 71.97; H,
6.44; N, 5.59; found C, 71.82; H, 6.28; N,
5.46).
−
1
+
1
639 (C -- -- -- O), 1575, 1508, 1377, 1226 cm .
H NMR (CDCl , 400 MHz): δ 0.77 & 0.93
2s, 12H, gem dimethyl), 1.84–2.09 (ABq, 4H,
1
3
(
J = 17.4 Hz, C ---CH ), 2.06–2.20 (Abq, 4H,
4
2
30 32
2
5
J = 16 Hz, C ---CH ), 3.90 (s,3H, ---OCH ),
2
2
3
5
.31 (s, 1H, C ---H), 7.03–7.12 (ABq, 4H, J =
9

754
Palani, Thirumalai, Ambalavanan, Ponnuswamy, and Ramakrishnan
Table 1. Crystal Data
Parameters
Empirical formula
CCDC No.
Formula weight
Temperature (K)
NTHA
NMTHA
C23H26N2O4
C30H32N2O5·CH3CH2OH
232064
394.46
293(2)
232065
544.63
293(2)
˚
Wavelength (MoKα) (A)
Crystal system
Space group
0.71073
Orthorhombic
P212121
0.71073
Monoclinic
P21/c
Unit cell dimensions
˚
a (A)
5.9716(1)
18.0476(3)
19.2445(2)
15.669(5)
10.652(4)
18.337(6)
108.25(1)
2906.66(2)
4
1.245
0.086
˚
b (A)
˚
c (A)
◦
β ( )
˚
3
Volume (A )
2074.04(5)
4
1.263
Z
−
3
Calculated density (Mg m
Absorption coefficient (mm 1)
)
−
0.087
F(000)
840
1160
Crystal size (mm)
θ-range for data collection ( )
Index ranges
0.48 × 0.46 × 0.22
1.50–26.00
−7 ≤ h ≤ 7
0.38 × 0.26 × 0.22
◦
2.00–26.00
−16 ≤ h ≤ 18
−12 ≤ k ≤ 12
−21 ≤ 1 ≤ 19
15871
5105 [Rint = 0.0925]
Full-matrix least-squares on F
5105/0/355
−
−
22 ≤ k ≤ 22
17 ≤ 1 ≤ 23
Reflections collected
Independent reflections
Refinement method
Data/restraints/parameters
Goodness-of-fit on F
12891
4078 [Rint = 0.0836]
Full-matrix least-squares on F
4078/0/268
2
2
2
0.959
0.989
Final R indices [I > 2σ(I)]
R indices (all data)
Largest diff. peak and hole (e A
R1 = 0.0521, wR2 = 0.1326
R1 = 0.0667, wR2 = 0.1413
0.264 and −0.310
R1 = 0.0725, wR2 = 0.1847
R1 = 0.1455, wR2 = 0.2157
0.454 and −0.371
˚
−3
)
Results and discussion
-(4-Nitrophenyl)-3,3,6,6-tetramethyl-3,4,6,
The compound NTHA showed bonds in
the IR spectrum corresponding to the N---H
−
1
−1
9
(3433 cm ), C -- -- -- O (1648 cm ) and ---NO
2
−
1
1
7
9
,9,10-hexahydro-1,8(2H,5H) acridinedione and
-(4-nitrophenyl)-10-(4-methoxyphenyl)-3,3,6,6-
(1846, 1367 cm ) groups. The H-NMR spec-
trum of NTHA showed two singlets at δ 1.08 and
0.93 due to geminal dimethyl groups, an AB quar-
tet between δ 2.05–2.22 with coupling constant
tetramethyl-3,4,6,7,9,10-hexahydro-1,8(2H, 5H)
acridinedione were synthesized by the reaction of
ꢁ
2
,2 -(4-nitrobenzylidene)bis(5,5-dimethyl cyclo-
J
= 16.11 Hz due to C ---CH protons, an an-
gem
2
2
hexane-1,3-dione) (1) with ammonium acetate
and p-anisidine (2) respectively in refluxing
acetic acid (Scheme 1).
other AB quartet between δ 2.33–2.45 with cou-
pling constant Jgem = 17.09 Hz due to C ---CH
4
2
protons, a singlet at δ 5.05 due to C proton, two
9
The compounds were obtained as crystalline
solids after recrystallization from chloro-
form:methanol (5:1) mixture and their structures
were confirmed by spectroscopic and X-ray
diffraction methods (Section 3 X-ray Crystal
Structure).
doublets between δ 7.47 and 8.03 with coupling
constant J = 8.79 Hz due to aromatic protons and
a singlet at δ 9.12 due to N---H proton.
The C-NMR spectrum showed peaks at δ
25.93, 28.38, 31.34, 33.33, 39.55, 49.52, 110.34,
121.88, 127.91, 144.65, 148.76, 153.56, and
13

Crystal structures of two acridinedione derivatives
755
˚
◦
◦
Table 2. Bond Lengths (A), Bond Angles ( ) and Torsion Angles ( ) for NTHA
Bond
X-ray
AM1
PM3
Bond
X-Ray
AM1
PM3
˚
Bond length (A)
C1 ---- C2
C1 ---- O16
C1 ---- C13
C2 ---- C3
C3 ---- C26
C3 ---- C27
C3 ---- C4
C4 ---- C14
C5 ---- C6
C5 ---- C11
C6 ---- C7
C6 ---- C28
C6 ---- C29
1.515(3)
1.225(3)
1.463(3)
1.528(3)
1.532(3)
1.527(3)
1.542(3)
1.485(3)
1.519(3)
1.498(3)
1.532(4)
1.529(4)
1.533(3)
1.565
1.550 C7 ---- C8
1.231 C8 ---- C12
1.509(4)
1.459(3)
1.234(3)
1.523(3)
1.522(3)
1.532(3)
1.374(3)
1.384(3)
1.335(3)
1.338(3)
1.474(4)
1.210(4)
1.232(4)
1.561
1.539
1.231
1.550
1.569
1.553
1.547
1.535
1.362
1.550
1.535
1.561
1.547
1.553
1.231
1.231
1.561
1.561
1.563
1.456
1.456
1.362
1.362
1.505
1.221
1.221
1.539
1.231
1.561
1.561
1.563
1.362
1.456
1.362
1.362
1.505
1.221
1.221
1.550 C8 ---- O15
1.565 C9 ---- C13
1.547 C9 ---- C12
1.547 C9 ---- C17
1.569 N10 ---- C11
1.535 N10 ---- C14
1.535 C11 ---- C12
1.539 C13 ---- C14
1.550 C20 ---- N23
1.553 N23 ---- O24
1.547 N23 ---- O25
◦
Bond angles ( )
O16 ---- C1 ---- C2
C1 ---- C2 ---- C3
C2 ---- C3 ---- C4
C2 ---- C3 ---- C26
C2 ---- C3 ---- C27
C3 ---- C4 ---- C14
C4 ---- C14 ---- N10
C5 ---- C11 ---- C12
C5 ---- C6 ---- C28
C6 ---- C7 ---- C8
C7 ---- C8 ---- C12
121.6(2)
113.3(2)
108.2(2)
110.2(2)
110.8(2)
112.5(2)
111.9(2)
125.6(2)
110.1(2)
115.1(2)
117.6(2)
119.49
114.39
109.84
109.16
110.53
115.15
117.69
122.65
110.54
114.41
118.58
119.49
C7 ---- C6 ---- C28
C7 ---- C8 ---- O15
C7 ---- C6 ---- C29
C9 ---- C17 ---- C18
C9 ---- C17 ---- C22
C13 ---- C9 ---- C17
C17 ---- C22 ---- C21
C21 ---- C20 ---- N23
C20 ---- N23 ---- O24
C20 ---- N23 ---- O25
110.3(2)
121.2(2)
109.6(2)
120.3(2)
121.4(2)
112.5(2)
120.9(2)
118.9(3)
119.1(3)
118.5(3)
109.69
119.49
109.16
121.96
119.14
111.11
120.54
120.68
121.18
121.18
11.53
119.49
109.15
119.14
121.96
111.10
120.53
120.64
121.18
121.18
114.39
109.85
109.15
110.52
115.18
117.69
122.66
109.96
114.39
118.57
◦
Torsion angles ( )
O16 ---- C1 ---- C2 ---- C3
C1 ---- C2 ---- C3 ---- C4
C1 ---- C2 ---- C3 ---- C26
C1 ---- C2 ---- C3 ---- C27
C2 ---- C3 ---- C4 ---- C14
C3 ---- C4 ---- C14 ---- C13
C12 ---- C8 ---- C7 ---- C6
C8 ---- C7 ---- C6 ---- C28
C8 ---- C7 ---- C6 ---- C29
−36.8(3)
55.7(3)
−63.8(3)
175.4(2)
−45.3(8)
17.2(3)
−30.0(2)
−67.3(2)
171.8(2)
−40.46
46.75
−75.47
166.69
−46.40
27.22
28.04
75.47
−166.69
44.35
−46.31
75.43
C9 ---- C12 ---- C8 ---- C7
C13 ---- C9 ---- C12 ---- C8
C9 ---- C12 ---- C11 ---- C5
C12 ---- C9 ---- C13 ---- C14
C3 ---- C4 ---- C14 ---- N10
C4 ---- C14 ---- C13 ---- C9
C21 ---- C20 ---- N23 ---- O24
C21 ---- C20 ---- N23 ---- O25
−177.6(2)
−156.2(2)
177.4(2)
−22.7(3)
−164.09(8)
−175.9(1)
4.1(5)
174.02
164.87
−174.48
14.90
−154.09
174.48
0.00
−173.84
−165.02
174.46
−166.73
−14.77
46.31
154.25
−27.10
−28.01
−75.43
166.73
−174.46
0.00
−179.99
−173.6(3)
−179.99
1
93.95 (C -- -- -- O). Mass spectrum shows a peak
and 3. A study of the results shows that the theo-
retically calculated values are in good agreement
with the experimental observation.
The ZORTEP plots of the molecules NTHA
and NMTHA are shown in Fig. 1a and b. The
central pyridine ring B of acridinedione moi-
ety tends to be planar, which is evident from
the π-conjugation along the bonds C12---C11---
N10---C14---C13 in both the molecules NTHA
at m/z 394 corresponding to the molecular ion.
The elemental analysis was concurrent with the
theoretical value. Similarly, the spectral and ana-
lytical data for the compound NMTHA were con-
sistent with the expected structure.
The crystallographic data for the compounds
NTHA and NMTHA are presented in Table 1. The
bond lengths, bond angles and torsion angles de-
rived from X-ray diffraction methods and calcu-
lated based on semiemprical methods for NTHA
and NMTHA for comparison are given in Tables 2
and NMTHA. This is evident from the conforma-
tion angles and bond lengths around the ring B as
detailed below:

756
Palani, Thirumalai, Ambalavanan, Ponnuswamy, and Ramakrishnan
˚
◦
◦
Table 3. Bond Lengths (A), Bond Angles ( ) and Torsion Angles ( ) for NMTHA
Bond
X-Ray AM1 PM3 Bond X-Ray
AM1
PM3
˚
Bond length (A)
C1 ---- C2
1.506(5)
1.546
1.503 C8 ---- C12
1.466(5)
1.544
1.518
C1 ---- O16
C2 ---- C3
C3 ---- C4
C3 ---- C26
C3 ---- C27
C4 ---- C14
C5 ---- C6
1.237(4)
1.531(5)
1.542(5)
1.530(5)
1.518(5)
1.505(4)
1.522(5)
1.505(5)
1.534(5)
1.533(5)
1.499(5)
1.231
1.566
1.566
1.547
1.553
1.554
1.555
1.546
1.553
1.547
1.546
1.220 C8 ---- O15
1.527 C9 ---- C12
1.528 C9 ---- C13
1.547 C9 ---- C17
1.544 N10 ---- C11
1.537 C11 ---- C12
1.537 C13 ---- C14
1.504 C20 ---- N23
1.544 N23 ---- O24
1.547 N23 ---- O25
1.504
1.231(4)
1.513(5)
1.507(4)
1.527(4)
1.410(4)
1.344(4)
1.346(4)
1.464(5)
1.244(4)
1.233(4)
1.232
1.551
1.551
1.565
1.501
1.364
1.364
1.505
1.221
1.221
1.220
1.523
1.524
1.537
1.469
1.366
1.368
1.412
1.262
1.289
C6 ---- C7
C6 ---- C28
C6 ---- C29
C7 ---- C8
◦
Bond angles ( )
O16 ---- C1 ---- C2
C1 ---- C2 ---- C3
C2 ---- C3 ---- C4
C2 ---- C3 ---- C26
C2 ---- C3 ---- C27
C3 ---- C4 ---- C14
C4 ---- C14 ---- N10
C4 ---- C14 ---- C13
C5 ---- C11 ---- C12
C6 ---- C7 ---- C8
C7 ---- C8 ---- O15
C7 ---- C6 ---- C28
C7 ---- C6 ---- C29
120.8(4)
119.01
114.42
109.03
110.78
109.36
116.47
120.75
119.58
119.47
114.44
118.94
109.32
110.78
119.01 C9 ---- C12 ---- C8
116.63 C9 ---- C12 ---- C11
107.93 C9 ---- C13 ---- C14
110.71 C9 ---- C17 ---- C18
110.71 C12 ---- C8 ---- C7
113.73 C13 ---- C9 ---- C12
117.74 C13 ---- C9 ---- C17
120.79 C17 ---- C18 ---- C19
121.19 C18 ---- C19 ---- C20
116.85 C19 ---- C20 ---- C21
119.56 C20 ---- N23 ---- O25
110.77 C20 ---- N23 ---- O24
108.93
117.2(3)
117.34
120.89
120.80
122.10
118.91
115.05
110.77
120.52
120.65
118.67
121.19
121.17
118.41
121.88
122.09
121.75
117.49
113.70
111.81
121.18
117.94
120.39
118.15
121.09
114.8(2)
107.1(3)
110.8(3)
110.1(3)
113.2(3)
115.9(3)
123.0(3)
122.6(3)
112.8(3)
121.6(3)
110.8(3)
109.4(3)
122.8(3)
122.7(3)
121.5(3)
117.9(3)
109.2(3)
111.8(3)
121.7(3)
118.1(3)
122.3(3)
117.0(4)
120.0(4)
◦
Torsion angles ( )
C1 ---- C2 ---- C3 ---- C4
C1 ---- C2 ---- C3 ---- C26
C1 ---- C2 ---- C3 ---- C27
C2 ---- C3 ---- C4 ---- C14
C3 ---- C4 ---- C14 ---- N10
C3 ---- C4 ---- C14 ---- C13
C12 ---- C8 ---- C7 ---- C6
C13 ---- C9 ---- C12 ---- C11
C13 ---- C9 ---- C12 ---- C8
−51.2(4)
68.7(4)
46.55
−75.51
166.28
−48.99
157.13
24.78
22.58
19.07
162.92
−49.41 C14 ---- N10 ---- C30 ---- C31
72.10 C9 ---- C12 ---- C8 ---- C7
−98.6(4)
−178.4(3)
−174.7(3)
21.1(4)
173.5(3)
6.3(5)
104.50
−174.94
176.68
−19.17
−173.66
−0.000
−179.95
0.26
−104.02
169.69
−174.94
1.78
−169.9(3)
−166.22 C9 ---- C12 ---- C11 ---- C5
52.59 C14 ---- C13 ---- C9 ---- C12
157.60 C4 ---- C14 ---- C13 ---- C9
−27.22 C19 ---- C20 ---- N23 ---- O24
50.3(4)
157.6(3)
−22.1(5)
−33.9(5)
−20.5(4)
159.7(3)
173.96
−0.051
179.92
−2.32
−18.54 C19 ---- C20 ---- N23 ---- O25 −175.4(4)
−1.06 C32 ---- C33 ---- O36 ---- C37
2.5(5)
178.97 C34 ---- C33 ---- O36 ---- C37 −177.1(3)
174.68
176.13
The planarity of the pyridine ring B is fur-
Atoms
NTHA
NMTHA
ther supported by the low value of the puckering
15
amplitudes QT = 0.265(2) and 0.220(3) when
compared with the values of the other A and C
rings for which QT = 0.466(2) and 0.455(2) for
NTHA, and 0.482(4) and 0.478(4) for NMTHA,
respectively.
◦
Conformation angles ( )
C9 ---- C12 ---- C11 ---- N10
C12 ---- C11 ---- N10 ---- C14
C11 ---- N10 ---- C14 ---- C13
N10 ---- C14 ---- C13 ---- C9
−3.6(3)
−16.8(3)
15.8(3)
5.5(3)
6.1(5)
10.6(5)
−10.1(4)
−7.2(5)
˚
Bond lengths (A)
In NTHA, the molecule contains a pseudo-
mirror plane, which is passing through the
atoms N10 and C9. A comparison of equiva-
lent bond lengths and torsion angles across the
C12 ---- C11
C11 ---- N10
N10 ---- C14
C14 ---- C13
1.335(3)
1.344(4)
1.374(3)
1.384(3)
1.338(3)
1.410(4)
1.405(4)
1.346(4)

Crystal structures of two acridinedione derivatives
757
situation was noted in related structures.16,17 In
NMTHA, the degree of folding was compara-
tively less and this is shown from dihedral angle
value between the pseudo-mirror plane which is
◦
1
0.2(1) .
The planarity of the nitrogroup is due to the
delocalization along the system. The bond dis-
tances [N23---O24 =] 1.210(4) A; 1.224(4) A and
˚
˚
[
N23---O25 =] 1.232(4) A; 1.233(4) A for NTHA
˚
˚
and NMTHA agree with the reported average val-
Fig. 1. (a) ZORTEP plot of the molecule NTHA with the
thermal ellipsoids are drawn at 30% probability level. (b)
ZORTEP plot of the molecule NMTHA with the thermal
ellipsoids are drawn at 30% probability level.
pseudo-mirror plane indicates the presence of
non-crystallographic symmetry element. The di-
hedral angle between the two mean planes passing
through the group of atoms [C1/C2/C3/C4/C14/
C13/C9/N10] and [C5/C6/C7/C8/C11/C12/C9/
◦
N10] is 24.3(1) and this implies that the acri-
Fig. 2. (a) Packing of the molecules in NTHA viewed down
the a-axis. (b) Packing of the molecules in NMTHA viewed
down the b-axis.
dine moiety is slightly folded about a line pass-
ing through N10 and C9. A similar kind of

758
Palani, Thirumalai, Ambalavanan, Ponnuswamy, and Ramakrishnan
˚
◦
Table 4. Hydrogen Bondings for NTHA [A & ( )]
∗
D ---- H
D· · ·A
H· · ·A
D--- H· · ·A
Sym
N10 ---- H10
N10· · ·O24 H10· · ·O24
N10 ---- H10· · ·O24
(1)
(2)
(2)
(1)
(3)
0
.860(1)
C5 ---- H5A
.970(2)
C22 ---- H22
.930(2)
C5 ---- H5B
.970(2)
C27 ---- H27B
3.257(3)
2.593(3)
134.8(1)
C5· · ·O15
H5A· · ·O15
C5 ---- H5A· · ·O15
0
3.726(3)
2.765(2)
170.9(1)
C22· · ·O16
3.413(3)
H22· · ·O16
2.531(1)
C22 ---- H22· · ·O16
0
158.6(1)
C5· · ·O24
H5B· · ·O24
C5 ---- H5B· · ·O24
0
3.806(4)
2.940(3)
149.1(1)
C27· · ·O15
3.720(3)
H27B· · ·O15 C27 ---- H27B· · ·O15
0
.960(2)
2.821(2) 156.2(1)
∗
Symmetry equivalent positions: (1) −x + 2, +y − 1/2, −z + 1/2; (2) x + 1,
y, +z; (3) −x + 1/2, −y + 1, +z − 1/2.
+
1
8–20
in agreement with the values observed for similar
structures.
In NTHA and NMTHA, the nitro group
shows a tendency to be coplanar with the phenyl
ring. This can be seen from the following confor-
mation angles:
˚
The C N bond
---
ues of 1.215 and 1.225 A.
24–26
lengths [C20---N23 =] 1.474(4) A and 1.464(5) A
˚
˚
are comparable with many of the p-substituted
2
1–23
nitrophenyl structures.
The keto bond lengths
---
˚
[
1
C8---O15 =] 1.234(3); 1.231(4) A; [C1 O16 =]
˚
.225(3); 1.237(4) A for NTHA and NMTHA are
˚
◦
Table 5. Hydrogen Bondings for NMTHA [A & ( )]
∗
D ---- H
D· · ·A
H· · ·A
D ---- H· · ·A
Sym
C4 ---- H4A
C4· · ·O24
3.678(5)
H4A· · ·O24
2.777(4)
C4 ---- H4A· · ·O24
(1)
(1)
(1)
(2)
(2)
(2)
(3)
(3)
(4)
(5)
(5)
0
.970(4)
C34 ---- H34
.930(4)
C37 ---- H37B
.960(2)
C31 ---- H31
.930(4)
C21 ---- H21
.930(5)
C22 ---- H22
.930(4)
C35 ---- H35
.930(4)
C27 ---- H27C
.960(5)
C28 ---- H28C
.960(5)
C38 ---- H38B
.960(2)
C38 ---- H38B
154.8(2)
C34· · ·O15
H34· · ·O15
C34 ---- H34· · ·O15
0
3.590(5)
2.699(3)
160.8(2)
C37· · ·O25
3.902(4)
H37B· · ·O25
2.971(3)
C37 ---- H37B· · ·O25
0
163.9(2)
C31· · ·O25
H31· · ·O25
C31 ---- H31· · ·O25
0
3.493(5)
2.591(3)
163.6(3)
C21· · ·O24
3.748(6)
H21· · ·O24
2.900(4)
C21 ---- H21· · ·O24
0
152.3(3)
C22· · ·O25
H22· · ·O25
C22 ---- H22· · ·O25
0
3.518(6)
2.801(4)
134.6(2)
C35· · ·O16
3.403(5)
H35· · ·O16
2.529(3)
C35 ---- H35· · ·O16
0
156.7(2)
C27· · ·O15
H27C· · ·O15
C27 ---- H27C· · ·O15
0
3.814(6)
2.920(3)
155.4(3)
C28· · ·O15
3.513(6)
H28C· · ·O15
2.582(3)
C28 ---- H28C· · ·O15
0
163.5(3)
C38· · ·O25
H38B· · ·O25
C38 ---- H38B· · ·O25
0
3.643(4)
2.750(4)
155.3(2)
C38· · ·N23
3.323(4)
H38B· · ·N23
2.563(3)
C38 ---- H38B· · ·N23
0
.960(2)
136.2(2)
∗
Symmetry equivalent positions: (1) x, +y − 1, +z; (2) −x − 1/2, +y − 1/2, −z + 1/2;
(
3) −x, −y + 2, −z; (4) −x + 1/2, +y − 1/2, −z + 1/2; (5) x + 1, +y − 1, +z.

Crystal structures of two acridinedione derivatives
759
Supplementary material NTHA: CCDC-232064 & NMTHA:
CCDC-232065 contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge via
www.ccdc.cam.ac.uk/conts/retrieving.html or from the Cambridge
Crystallographic Data Centre, 12, Union Road, Cambridge CB2
1EZ, United Kingdom; Fax: (+44) 1223-336-033: e-mail: deposit@
ccdc.cam.ac.uk.
Atoms
NTHA
NMTHA
◦
◦
C19 ---- C20 ---- N23 ---- O24
C19 ---- C20 ---- N23 ---- O25
C21 ---- C20 ---- N23 ---- O24
C21 ---- C20 ---- N23 ---- O25
−176.5(4)
6.3(5)
◦
◦
◦
◦
5.8(4)
−172.1(4)
◦
◦
4.1(5)
−175.4(4)
6.3(6)
−173.6(3)
Acknowledgments
The nitrophenyl group is approximately per-
One of the authors P. Ambalavanan thanks
UGC for providing FIP under IX plan period
and also the Commissioner of Collegiate Edu-
cation, Chennai 600 006 for giving permission
to carry out the research work in the Department
of Crystallography and Biophysics, University of
Madras.
pendicular to the pyridine ring B (the subtending
◦
◦
angles are 89.7(1) for NTHA and 88.9(1) for
NMTHA) and this may be due to the steric hin-
drance between the keto oxygens.
In NTHA, the dimethyl groups attached to
the rings A and C adopt axial and equatorial ori-
entations, which is evident from the torsion an-
◦
gles [C26---C3---C4---C14] = 74.7(2) , [C27---
References
◦
C3---C4---C14] = −166.0(2) , [C11---C5---C6---
◦
C28] = 69.6(3) and [C11---C5---C6---C29] =
1
2
3
4
. Talacki, R.; Carrel, H.L.; Glusker, J.P. Acta Cryst. 1974, B30,
◦
−
169.6(2) . In NMTHA, a similar situation exists
1044.
. Acheson, R.M. The Acridines; 1st ed., Arnold Press: London,
for the dimethyl groups attached to the rings A
and C. The torsion angles: [C26---C3---C4---C14]
1
956.
. Prasad Krishna, B.N.; Banasal, I.; Das, P.; Srivastava, R. Curr.
Sci. 1984, 53, 778.
. Asthana, P.; Rastogi, S.; Ghose, S.; Das, S.R. Indian. J. Chem.
◦
◦
=
−70.2(4) , [C27---C3---C4---C14] = 169.5(3) ,
◦
[
C11---C5---C6---C29] = 70.6(4) and [C11---
1
991, 30B, 893.
5. Fan, J.Y.; Tercel, M.; Denny, W.A. Anti-Cancer Drug Des. 1997,
2, 277.
◦
C5---C6---C28] = −169.6(3) confirm the ax-
1
ial and equatorial orientations in this molecule
also.
6
. Albert, A. The Acridines; 2nd ed., Edward Arnold: London,
1966.
7
. Waring, M.J. The Molecular Basis of Antibiotic Action; John
The packing of the molecules in the unit cell
for NTHA and NMTHA are shown in Fig. 2a and
b. In NTHA, the N---H group (N10---H10) forms
Wiley: London, 1972.
8. Neidle, S. Prog. Med. Chem. 1979, 16, 151.
. Lerman, L.S. J. Mol. Biol. 1961, 3, 18.
0. Siemens, SMART Software Reference Manual; Siemens
Analytical X-ray Instruments Inc. Madison, Wisconsin, USA,
9
1
hydrogen bonding with the nitro-oxygen substi-
tuted at C9-position. The details are: N10---H10 =
1996.
1
1. Sheldrick, G.M., SHELXS97, Program for the Crystal Structure
˚
---
0
1
.860(1) A, N10 O24 (−x + 2, y − 1/2, −z +
Solution, University of Gottingen, Germany, 1997.
12. Sheldrick, G.M., SHELXL97, Program for the Crystal Structure
˚
---
˚
/2) = 3.257(3) A, H10 O24 = 2.593(3) A and
◦
Refinement, University of Gottingen, Germany, 1993.
3. Nardelli, M.; Comput. Chem. 1983, 7, 95.
an angle of N10---H10· · ·O24 = 134.8(1) . In-
1
teresting to note that this hydrogen bond plays a
major role in exhibiting polymeric chains along
b-direction. In NMTHA, the molecules in the unit
cell are packed in a discrete fashion. However
the atom C38 of the solvent molecule forms an
interaction with the N23 atom of the nitrogroup.
The keto oxygens O15 and O16 are also involved
in C---H· · ·O type of intermolecular interactions.
14. Zsolnai, L., ZORTEP, An Interactive Graphics Crystal Structure
Illustrations, University of Heidelberg, Germany, 1997.
5. Carpy, A.; Leger, J.M.; Mountagut, M.; Nuhrich, A. Cryst.
Struct. Comm. 1977, 6, 741.
1
1
1
1
6. Carpy, A.; Leger, J.M.; Nuhrich, A. Cryst. Struct. Comm. 1978,
7
, 187.
7. Allen, F.H.; Kennard, O.; Watson, D.G.; Brummer, L.; Orpen,
A.G.; Taylor, R. J. Chem. Soc. Perkin Trans. II, 1987, S1.
8. Eswaramoorthy, S. Ph. D. Thesis; University of Madras:
Chennai, India, 1992.
19. Vincent, A.T.; Wheatley, P.J. J. Chem. Soc. Perkin II 1972,
1
567.
The details of the hydrogen bondings are given in
Tables 4 and 5.
2
0. Guttormson, R.; Robertson, B.E. Acta Cryst. 1972, B28, 2702–
2708.

760
Palani, Thirumalai, Ambalavanan, Ponnuswamy, and Ramakrishnan
2
2
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24. Sivaraman, J.; Subramanian, K.; Velmurugan, D.; Subramanian,
E.; Shanmugasundaram, P.S. Acta Cryst. 1996, C52, 481.
25. Cremer, D.; Pople, J.A. J. Am. Chem. Soc. 1975, 97, 1354.
26. Gunasekaran, K.; Velmurugan, D.; Murugan, P.; Ramakrishnan,
V.T.; Panneerselvam, K.; Soriano-Garcia, M. Acta Cryst. 1996,
C52, 2609.
Ramasubbu, N. Acta Cryst. 1998, C54, 1534.
2. Ganesh, V.K.; Banumathi, S.; Velmurugan, D.; Ramasubbu, N.;
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3. Didberg, O.; Campsteyn, H.; Dupont, L. Acta Cryst. 1973, B29,
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03.